KR102001108B1 - Silane Crosslinkable Polymer Composition - Google Patents

Abstract

The present invention relates to a crosslinkable polymer composition comprising a polyolefin (a) containing a hydrolyzable silane group and a silanol condensation catalyst compound, and also to an article, preferably a cable, to which said composition is applied. The invention also provides a method of using a silanol condensation catalyst compound for cross-linking a product, preferably a layer of cable.

Description

Silane Crosslinkable Polymer Composition < RTI ID = 0.0 >

The present invention relates to a polymer composition comprising a polyolefin containing a hydrolyzable silane group and a silanol condensation catalyst, a product, preferably the use of said composition for the production of a cable, a product, preferably a silane- Cross-linked products comprising the polymer composition, preferably a cable, a product comprising the composition, preferably a cable and a silane-crosslinked product comprising the silane-crosslinked polymer composition, preferably a silane- ≪ / RTI >

Typical cables for wire and cable (W & C) applications include conductors surrounded by a layer of one or more polymeric materials. The cable is generally manufactured by extruding a conductor layer. One or more of these layers are often cross-linked to improve the resistance to deformation at high temperatures as well as mechanical strength and / or chemical resistance in the layers of the cable.

Cross-linking of the polymer may be by a free radical reaction using, for example, cross-linking reagents which are radiation or free radical generating reagents; Can be carried out through the hydrolyzable silane group in the polymer using a condensation catalyst in the presence of moisture.

A power cable is defined as a cable that operates at any voltage level to transmit energy. The voltage applied to the power cable may be AC, alternating, direct current (DC), or transient (transient or impulsive). Power cables are also typically referred to by well known terminology such as low voltage (LV), medium voltage (MV), high voltage (HV) or ultra high voltage (EHV) power cables, depending on the level of their operating voltage do. A power cable is defined as a cable that conducts energy at any voltage level and typically operates at voltages higher than 100V. Low-voltage (LV) power cables typically operate at voltages below 3 kV. Medium voltage (MV) and high voltage (HV) power cables are typically higher than low voltage (LV) cables and operate in a variety of applications. Typical medium voltage (MV) power cables typically operate at 3 to 36 kV, and typical high voltage (HV) power cables operate at voltages higher than 36 kV. Very high voltage (EHV) power cables typically operate at higher voltages than high voltage (HV) power cables are used. Embodiments of low voltage (LV) power cables and some intermediate voltage (MV) power cables generally include an electrical conductor covered with an insulator layer. Typically, medium voltage (MV) and high voltage (HV) power cables include conductors that are surrounded in sequence by at least an inner semiconductor layer, an insulator layer, and an outer insulator layer.

Silane-curing materials are used today primarily as insulator layers in low-voltage cables and as insulator layers and semiconductor layers in medium- to high-voltage cables.

When the polymer composition is cross-linked through a hydrolyzable silane group, the hydrolyzable silane group may be copolymerized with a silane group comprising a monomer such as olefin and a comonomer, May be introduced into the polymer by grafting the silane groups involved. Grafting is a chemical modification of the polymer by the addition of a silane group, which generally comprises a compound in a radical reaction. Silane groups containing such comonomers and compounds are well known in the art and can be obtained commercially. The hydrolyzable silane groups are cross-linked by hydrolysis, and a series of condensation in the presence of a silanol condensation catalyst and water (H ₂ O), as typically known in the art. Silane cross-linking techniques are known and described in US 4,413,066, US 4,297,310, US 4,351,876, US 4,397,981, US 4,446,283 and US 4,456,704.

For the cross-linking of polyolefins containing hydrolyzable silane groups, silanol condensation catalysts must be used. Conventional catalysts include, for example, tin-, zinc-, iron-, lead-, and the like, such as dibutyltin dilaurate (DBTDL) ) Or a cobalt- (cobalt-) organic compound. However, DBTDL is known to have a negative impact on the natural environment when cross-linked products such as cables are installed on the ground. It is also a dangerous material to work with.

CA50288 describes a titanium (Ti) catalyst for cured epoxy functionalized polymers. GB1377737 describes polyolefin grafting with UV radiation in conjunction with silane compounds. The grafted polyolefin is then cross-linked with a metal carboxylate, a titanium ester or a titanium chelate. The catalyst used in this example is dibutyltin laurate. It does not mention how to use it in wire and cable (W & C) applications. WO2007032885 describes titanium catalysts for wire and cable (W & C) applications.

For this reason, it is an object of the present invention to provide additional silanol condensation catalysts for polymer compositions comprising polyolefins containing hydrolyzable silane groups, which avoid the disadvantages of DBTDL, i.e., are more environmentally friendly and less dangerous to work .

Recently, surprisingly, this object has been achieved with a new type of silanol condensation catalyst which is very useful for its products, which are layers of silane crosslinking polymer compositions and preferably cables.

Therefore,

(a) a polyolefin containing a hydrolyzable silane group and

(b) a silanol condensation catalyst compound of formula (I)

Lt; RTI ID = 0.0 > of: < / RTI &

Me ^{+ n} (OCR ¹ = CR ² - (C = O) R ³ ) _m R ⁴ _s (I),

In the above formula, Me is a metal selected from group 2 to 14 of the periodic table (according to the inorganic chemical 1989 IUPAC nomenclature);

n is an integer of from 1 to 6; Preferably 1 to 4;

m is an integer between 1 and 6; Preferably 1 to 4;

s is an integer between 0 and 5; Preferably 0 to 3;

Wherein m + s = n and n is an integer of 1 to 6; Preferably 1 to 4;

Each R < ¹ > is independently H; A substituted or unsubstituted saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; A substituted or unsubstituted, aromatic hydrocarbyl group optionally containing one or more heteroatoms; Or a functional group;

Each R < ² > is independently H; A substituted or unsubstituted saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; An aromatic hydrocarbyl group optionally substituted with one or more heteroatoms; Or a functional group;

Each R < ³ > is independently H; A substituted or unsubstituted saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; An aromatic hydrocarbyl group optionally substituted with one or more heteroatoms; Or a functional group;

Or any two of R < ¹ >, R < ² > and R < ³ > form a ring system with the atoms to which they are attached;

And

Each R ⁴ is independently a substituted or unsubstituted saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; An aromatic hydrocarbyl group optionally substituted with one or more heteroatoms; A hydrolyzable group for Broensted acid; = O; Or a halogen atom.

The silanol condensation catalyst compounds of formula (I) (b) are, for example, more environmentally friendly catalysts than tin based catalysts. The compounds of formula (I) unexpectedly have a good cross-linking efficiency, expressed as a hot set property or a gel content, as defined below under the "measuring method ". The silanol condensation catalyst compound of formula (I) (b) surprisingly can preferably be used as an industrially suitable amount of a cross-linking catalyst for producing cross-linked products which are preferably cable layers with the mechanical properties required for power cables . The cross-linked polymer compositions of the present invention also have good electrical properties required in the wire and cable (W & C) field.

The polymer compositions of the present invention as defined above or below are referred to herein as "polymer compositions ". As the constitution of the polymer composition, the polyolefin (a) containing a hydrolyzable silane group is referred to as "polyolefin (a)" herein and the silanol condensation catalyst compound of the formula (I) (b) ","compound of formula (I) ",or" compound (I) ".

In addition, the catalyst (b) may be present in the molded article, preferably before or after the formation of the cable layer, in the polymer composition.

The preferred product is a cable. Cables refer to cables and wires.

The preferred cable includes a conductor surrounded by at least one layer selected from an insulator layer, a semiconductor layer or a jacketing layer. More preferably, the at least one layer is an insulator layer.

A more preferred cable is a power cable comprising a conductor surrounded by at least an inner semiconductor layer, an insulator layer and an outer semiconductor layer, wherein at least one insulator layer or one or more inner and outer semiconductor layers, preferably at least one insulator layer, Is preferably

(a) a polyolefin containing hydrolysable silane groups and

(b) a silanol condensation catalyst compound which is a silanol condensation catalyst (b) which is a compound of formula (I) as defined above or below,

≪ RTI ID = 0.0 > and / or < / RTI >

Naturally, the polymer composition may comprise two or more catalysts (b).

The product, preferably the cable, is cross-linkable and is continuously cross-linked before final application. Cross-linkability means that the polymer composition can be silane-crosslinked using catalyst (b), preferably before the product is used in its final application.

The present invention also relates to a process for cross-linking one or more layers of a cable comprising cross-linking of a polyolefin (a) as defined above or hereinafter, more preferably a product, preferably a polyolefin (a) (I) as defined below.

Also provided is an article comprising the polymer composition, preferably a cable and a method of making the same. Preferably one or more layers of the preferred cable, including the product, preferably the polymer composition, are silane-crosslinked.

The following preferred embodiments, properties and subgroups of polyolefin (a) and compounds of formula (I), polymer compositions and preferably cables are products that can be independently generalized, and in any order or combination, Can be used to further clarify the preferred embodiments of the composition and preferably the cable. In addition, unless otherwise specified, the description of the polyolefin (a) is clearly applicable to selective cross-linking prior to the polyolefin.

The silanol condensation catalyst compound (b) (= compound of formula (I)) of the formula (I)

The catalyst (b) is an organic compound which catalyzes the cross-linking of the silane group through hydrolysis and the continuous condensation reaction in the presence of the catalyst (b) as mentioned above or below.

-OCR ¹ = CR ² of formula (I), without limitation of any hypothesis - (C = O) R ^{3 group} is is believed that the conjugated double bond system (conjugated), there is a covalent bond delocalization (delocalised) can be have.

In compound (I), the hydrocarbyl group may be linear, branched or cyclic or cyclic and linear or branched. For the avoidance of doubt, it is evident from the definition used herein that "hydrocarbyl" does not denote aromatic cyclic groups in this specification. That is, the aromatic cyclic group is defined as an aromatic hydrocarbyl. "Partially unsaturated" means that the moiety may contain one or more double or triple bonds and may contain an alkenyl radical comprising one or more double bonds and an alkynyl (including one or more triple bonds) ) ≪ / RTI > radicals. In the case of "partially unsaturated cyclic hydrocarbyl ", the term " partially unsaturated" ring moiety is non-aromatic to distinguish it from "aromatic rings" such as phenyl or pyridyl radicals, There may be a combination.

Monocyclic includes monocyclic ring systems such as cyclopentyl, cyclohexyl, cycloheptyl or phenyl. Multicyclic refers herein to a fused ring system comprising a bicyclic ring such as naphthyl.

"Optional" in compound (I) means that it may or may not be present. For example, an optional substitution indicates the possibility that the substitution may or may not be present. "Unsubstituted" means, of course, that no substitution exists.

Each of the preferred subgroups of substituents may be generalized and may be combined in any combination in the compounds of formula (I).

Also, optional heteroatoms which may be present in any substituent as moieties in a ring system formed by two substituents in the substituent or by the two substituents as defined above or below are independently N, O, P , Or S, and is preferably selected from N, O or S, more preferably from N or O, most preferably O. N, P or S may be present as an oxide, such as SO ₂ . The position of the heteroatom is not limited. A hydrocarbyl substituent comprising a heteroatom may for example be linked to the backbone of the subcombination (I), or the hydrocarbyl substituent may be interrupted by one or more heteroatoms. N or O, preferably O, if present in a hydrocarbyl substituent, can disrupt the hydrocarbyl moiety of compound (I) (e.g., present as NX-, wherein X is as defined above or below , Or a hydrocarbyl substituent is attached to the backbone of compound (I) via an N or O atom, preferably an O atom. That is, the hydrocarbyl substituent is N = Z, -NH-Z, N (Z) ₂ , or -OZ; Where each Z moiety independently refers to the rest of the hydrocarbyl substituent other than H (the remainder may further include a heteroatom such as O which interrupts the hardrockyl group). Hydrocarbyls, as used herein, that contain one or more heteroatoms are often named according to their function organochemically. For example, the N or O, including hydrocarbyl, is defined as an amine or an imine (including one or more hydrocarbyl moieties herein) and ethers (e.g., alkoxy or alkylalkoxy groups), respectively. do. However, in the present specification, a hetero atom which cuts off a hydrocarbyl substituent or connects a hydrocarbyl substituent to the skeleton of a compound is not limited to a hydrocarbyl substituent of the compound (I) in order to emphasize the presence of at least one hydrocarbyl moiety in the hydrocarbyl substituent of the compound Carvings. "

An optionally substituted saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as R ¹ , R ² , R ³ or R ⁴ substituent of compound (I) as defined above or below When present, the hydrocarbyl group is more preferably

(i) optionally a linear or branched, saturated or partially unsaturated hydrocarbyl group;

(ii) a saturated or partially unsaturated hydrocarbyl group optionally substituted linear or branched, containing a saturated or partially unsaturated cyclic hydrocarbyl moiety, or an optionally linear or branched, aromatic hydrocarbyl moyer A saturated or partially unsaturated hydrocarbyl group containing a thiol; A saturated or partially unsaturated hydrocarbyl group containing a saturated or partially unsaturated cyclic hydrocarbyl moiety, optionally linearly or branched, optionally substituted; or

(iii) an optionally substituted saturated or partially unsaturated cyclic hydrocarbyl group.

Preferably, when the cyclic system (iii) or the saturated or partially unsaturated cyclic hydrocarbyl moiety is present in the hydrocarbyl (ii), it contains 5 to 15 ring atoms, more preferably 5 to 15, Is a saturated or partially unsaturated mono- or multicyclic hydrocarbyl ring system which has 12 carbon atoms and may comprise one or more heteroatoms as defined above and even more preferably is a saturated or partially unsaturated, Is a saturated or partially unsaturated monocyclic hydrocarbyl ring having 5 to 7 ring atoms.

As each of optionally substituted saturated or partially unsaturated hydrocarbyl groups each of the above selection (i), (ii), and (iii) may independently comprise one or more heteroatoms as mentioned above, Preferably one or two atoms, which are preferably independently selected from O or N, preferably O atoms.

As defined above, when present in the hydrocarbyl (ii) of the compound (I) as an R ¹ , R ² , R ³ or R ⁴ substituent or as an aromatic hydrocarbyl moiety, Mono or multicyclic aryl which has 12 ring atoms and may contain one or more heteroatoms as defined above, more preferably mono or multicyclic aryl having carbon ring atoms, more preferably Is a phenyl moiety.

The aromatic hydrocarbyl group may optionally contain one or more substituents and, if present, is preferably a functional group as defined below or an optionally substituted linear or branched group as defined above and is saturated or partially unsaturated (I) < / RTI >

When either of R ¹ , R ² and R ³ as defined above in compound (I) forms a substituted or unsubstituted ring system with the atoms to which they are attached, the ring system is preferably saturated Or a partially unsaturated aromatic ring which is optionally fused with one or more other rings wherein said ring and optionally fused ring system optionally contain further heteroatoms and may be optionally substituted. Preferably such a ring system comprises 5 to 15 ring atoms, more preferably a substituted or unsubstituted, saturated, partially unsaturated or aromatic mono or multicyclic ring system, said mono or multicyclic ring system Is an aromatic mono or multicyclic ring system having 5 to 12 ring atoms, preferably 5 to 10 ring atoms, more preferably a substituted or unsubstituted, saturated, partially unsaturated or 5 to 7 ring atoms , Which is optionally fused with another ring system and may contain one or more heteroatoms as defined above or below.

Also, any of the "optionally substituted" linear or branched, saturated or partially unsaturated hydrocarbyl groups (i), hydrocarbyl optionally as a substituent according to option (iii), or hydrocarbyl according to hydrocarbyl option (ii) Any of the "optionally substituted" saturated or partially unsaturated cyclic hydrocarbyl groups as moieties in the substituents; Either as a substituent or as an "optionally substituted" aromatic hydrocarbyl as the moiety in the hydrocarbyl option (ii); Or any of the "optionally substituted" ring systems formed by any two of R ¹ , R ² or R ³ of Compound I, including its preferred subgrop as defined above or below, The "optional substituent" is preferably selected from a "functional group", which is well known and refers to a pendant group, such as, for example, a substituent attached to a phenyl ring. The number of optional functional groups is preferably 1 to 4, preferably 1 to 3, more preferably 1 or 2. Optionally functional groups are independently OH, -NH _2, = NH, nitro (nitro), chiol (thiol), Bang C _1-12 alkyl (thioC _1-12 alkyl), CN or F, -Cl, -Br or I and will selected from the same halogen, -COR, -CONR _2, the group consisting of -COOR, where each R 'is independently H or (C1-C12) alkyl.

Also, as a substituent according to the hydrocarbyl option (iii) or as a moiety of a hydrocarbyl substituent according to the hydrocarbyl option (ii), a saturated or partially saturated cyclic hydrocarbyl group; An aromatic hydrocarbyl as a substituent or as a moiety of the hydrocarbyl option (ii); Or a ring system formed by any two of R ¹ , R ² or R ³ of compound (I) comprising its preferred subgrop as defined above or below, May include a linear or branched, saturated or partially unsaturated hydrocarbyl group (i) optionally substituted as an "optional" substituent as defined hereinbefore or hereinafter, with respect to the functional group as the "optional" More preferably a linear or branched (C1-C20) alkyl group, more preferably a linear or branched (C1-C12) alkyl group, more preferably a linear or branched (C1-C6) alkyl group; Or any mixture of said functional groups and hydrocarbyl groups.

It is noted that the "functional group" as an "optional" substituent is different from the "hydrocarbyl" substituent comprising a "heteroatom" of the compound (I). As the catalyst compound (b), the compound (I) can be used by purchasing a commercial product and can be prepared according to the process described in the chemical literature or a similar process.

More preferably, as defined above,

A preferred subgroup of compound (I) of formula Me ^{+ n} (OCR ¹ ═CR ² - (C═O) R ³ ) _m R ⁴ _s (I) is a compound of formula (Ia) Referred to herein as compounds; Me is preferably a metal selected from the group consisting of 3 to 14, preferably 4 to 14, preferably 4 to 12, groups of 3 to 6, preferably 4 or 5, cycles on the periodic table (according to the inorganic chemical 1989 IUPAC nomenclature);

n is an integer from 2 to 4, preferably 2 or 4;

m is 1 to 3, preferably 1 or 2, more preferably 2;

s is an integer from 0 to 3, preferably 0, 1, or 2, more preferably 0 or 2; m + s = n;

Each R < ¹ > is independently H; A substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; Or a substituted or unsubstituted, aromatic hydrocarbyl group optionally containing one or more heteroatoms;

Each R < ² > is independently H; A substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; Or an optionally substituted or unsubstituted aromatic hydrocarbyl group comprising at least one heteroatom;

Each R < ³ > is independently H; A substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; Or a substituted or unsubstituted aromatic hydrocarbyl group optionally containing one or more heteroatoms;

Each R < ⁴ > is independently H; A substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms; A group hydrolyzed to Broensted acid; = O; F, Cl, Br or I.

As defined above, the more preferred azides of the particular subgrop (Ia) of the compound (I) of the formula Me ^{+ n} (OCR ¹ ═CR ² - (C═O) R ³ ) _m R ⁴ _s subgroup) is referred to herein as a compound of formula (Ib) which is a compound of formula (Ia) wherein:

Me is a metal selected from Groups 3 to 12 of the Periodic Table (according to Inorganic Chemistry 1989 IUPAC nomenclature) of 4 to 6 cycles, preferably 4 or 5 cycles, more preferably 4 cycles;

n is an integer from 2 to 4, preferably 2 or 4;

m is 1 to 3, preferably 1 or 2, more preferably 2;

s is 0 to 3, preferably 0, 1, or 2, more preferably 0 or 2; m + s = n;

Each R < ¹ > is independently H; Or -X _w -R ^{1 '} , wherein X is a heteroatom, preferably N, O, P or S, more preferably N or O, more preferably O, as defined above; w is 0 or w is 1; R ¹ 'is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as defined above or below, or an optionally substituted one or more heteroatoms as defined above or below, A substituted or unsubstituted aromatic hydrocarbyl group containing an atom;

Each R < ² > is independently H; or

-X _w -R ^{1 '} , wherein X is a heteroatom, preferably N, O, P or S, more preferably N or O, more preferably O, as defined above; w is 0 or w is 1; And R ¹ 'is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as defined above or below, or an optionally substituted one or more A substituted or unsubstituted aromatic hydrocarbyl group containing a hetero atom;

Each R < ³ > is independently H; or

-X _w -R ¹ ', wherein X is a heteroatom, preferably N, O, P or S, more preferably N or O, more preferably O, as defined above; w is 0 or w is 1; And R ¹ 'is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as defined above or below, or an optionally substituted one or more A substituted or unsubstituted aromatic hydrocarbyl group containing a hetero atom;

Each R < ⁴ >

-X _w -R ¹ ', wherein X is a heteroatom, preferably N, O, P or S, more preferably N or O, more preferably O, as defined above; w is 0 or w is 1; And R ¹ 'is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as defined above or below, or an optionally substituted one or more A substituted or unsubstituted aromatic hydrocarbyl group containing a hetero atom;

A group hydrolyzed by Broensted acid selected from -Y-R2; Y is preferably OC (= O) -, -C (= O) -OC (= O) -, -NR 5 C (= O) -, -OC (= O) NR 5 -, -OC (= O ^{) O-, -NR 5 C (=} O) OR -, - C (= O) NC (= O) -, - OS (= O) 2 -, - OP (= O) 2 -, -NR 5 S _{(= O) 2 -, -OS} (= O) 2 NR 5 -, -SC (= O) -, -OPR 6 (= O) O -, - OP (= O) (oR 6) O-, or OPR ⁶ (= O) OP (= O) (OR 2) O- wherein each R ⁵ is independently H or a linear hydrocarbyl group, preferably a (C 1 -C 8) alkyl group, more preferably R ⁵ is H ; And each R < ⁶ > is independently H or R2, as defined below; Each R2 is independently a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms as defined above or below; Or a substituted or unsubstituted aromatic hydrocarbyl group optionally containing one or more heteroatoms as defined above or below,

- = O;

Or chlorine (Cl).

Of R ¹ to R ³ substituent R1 moiety or compound (Ia) and (Ib) preferred subgroup (subgroup) as R1 or R2 moieties in the R ² substituent of the compound (I) containing a substituted or unsubstituted saturated Or partially unsaturated, optionally containing one or more heteroatoms, are each independently selected from the group consisting of:

An optionally substituted linear or branched hydrocarbyl group (i) as defined above; It is preferably an optionally substituted linear or branched (C1-C50) alkyl group, an optionally substituted linear or branched (C2-C50) alkyl group or an optionally substituted linear or branched (C2-C30) alkyl group; More preferably a linear or branched (C1-C50) alkyl group, preferably a linear or branched (C1-C30) alkyl group, more preferably a linear or branched (C1-C20) alkyl group;

- linear or branched (C1-C20) alkyl (O- (C1-C20) alkyl) _p, (C1-C20) alkyl (O- (C1-C20) alkenyl) _p or (C1-C20) alkyl, -O (C1-C20) alkyl) _e (C1-C20) alkenyl) _f, wherein each p is independently 1, 2, or 3, each e is independently 0, 1, or 2, and each f is independently 0, 1 or 2; This is preferably a linear or branched (C1-C12) alkyl (O- (C1-C12) alkyl) _p or (C1-C12) alkyl (O- (C1-C12) alkenyl) _p, wherein each p is independently 1 or 2; or

An optionally substituted mono- or multicyclic aryl group, preferably an optionally substituted mono- or multicyclic aryl group, which has 6 to 12 ring atoms and which may comprise one or more heteroatoms as defined above, Carbon ring atoms, more preferably an optionally substituted mono or multicyclic aryl group having an optionally substituted phenyl group.

The aromatic hydrocarbyl group as R1 or R2 is optionally substituted with preferably 1 to 4, preferably 1 or 2, more preferably 1 substituent, each of these substituents being independently optionally substituted as defined above (C1-C60) alkyl group, more preferably a linear or branched (C1-C30) alkyl group, even more preferably a linear or branched, saturated or partially unsaturated hydrocarbyl group, preferably a linear or branched ) Alkyl group.

(Ib) of formula (I) of formula (Me ^{) with the} formula Me ^{+ n} (OCR ¹ ═CR ² - (C═O) R ³ ) _m R ⁴ _s A preferred subgroup is referred to herein as a compound of formula (Ic)

Me ^{+ n} (OCR ¹ = CH- (C = O) R ³ ) _m R ⁴ _s (Ic)

Wherein Me is selected from a metal selected from 4 groups of 3 to 12 members on the Periodic Table (according to the Inorganic Chemistry 1989 IUPAC nomenclature);

n is 2 or 4;

m is 2; s is 0 or 2; m + s = n;

Each R ¹ is independently -X _w -R ¹ ', wherein X is preferably N, O, P or S, more preferably N or O, even more preferably O A heteroatom; w is 0 or 1, preferably 0; The R ¹ 'moiety is preferably selected from linear or branched (C ¹ -C 30) alkyl groups, more preferably linear or branched (C 1 -C 20) alkyl groups, more preferably linear or branched (C 1 -C 12) Lt; / RTI > is selected from linear or branched (C1-C6) alkyl groups;

Each R ³ is independently -X _w -R ¹ ', wherein X is preferably N, O, P or S, more preferably N or O, even more preferably O A heteroatom; w is 0 or 1, preferably 0; The R ¹ 'moiety is preferably selected from linear or branched (C ¹ -C 30) alkyl groups, more preferably linear or branched (C 1 -C 20) alkyl groups, more preferably linear or branched (C 1 -C 12) Lt; / RTI > is selected from linear or branched (C1-C6) alkyl groups;

Each R < ⁴ >

(1) X _w -R ^{1 '} , wherein X is a heteroatom, preferably N, O, P or S, more preferably N or O, more preferably O, as defined above or below; w is 0 or 1, preferably 0; The R1 moiety

More preferably a linear or branched (C1-C20) alkyl group, more preferably a linear or branched (C1-C12) alkyl group, more preferably a linear or branched (C1-C6) alkyl group; or

- linear or branched (C1-C20) alkyl (O- (C1-C20) alkyl) _p, (C1-C20) alkyl (O- (C1-C20) alkenyl) _p or (C1-C20) alkyl, -O (C1-C20) alkyl) _e (C1-C20) alkenyl) _f, wherein each p is independently 1, 2 or 3, each e is independently 0, 1 or 2, and each f is independently 0, 1 or 2; Preferably a linear or branched (C1-C12) alkyl (O- (C1-C12) alkyl) _p or (C1-C12) alkyl (O- (C1-C12) alkenyl) _p, and more preferably linear or branched, (O- (CrC6) alkyl) _p or (CrC6) alkyl (O- (CrC6) alkenyl) _p wherein each p is independently 1 or 2 Selected;

More preferably, the R < ¹ &^gt; moiety is

More preferably a linear or branched (C1-C20) alkyl group, more preferably a linear or branched (C1-C12) alkyl group, more preferably a linear or branched (C1- C6) alkyl group;

2 is as defined above, OC (= O) -R2, -OP (= O) 2 -R2, -OPR 6 (= O) OP (= O) (O-R2) 2 ( where R ^6, preferably H), -OP (= O) (oR 6) O-R2 ( wherein R ⁶ is, R2) as preferably defined above or below, or -OS (= O as defined above) ₂ - A group hydrolyzed to Bronsted acid selected from R2-; And the R2 moiety

A substituted or unsubstituted, saturated or partially unsaturated, hydrocarbyl group optionally containing one or more heteroatoms as defined above; An optionally substituted linear or branched (C1-C50) alkyl group, an optionally substituted linear or branched (C2-C50) alkyl group or an optionally substituted linear or branched (C2-C30) alkyl group; More preferably from a linear or branched (C1-C50) alkyl group, even more preferably from a linear or branched (C1-C30) alkyl group, even more preferably from a linear or branched (C1-C20) alkyl group; or

Any substituted mono or multicyclic aryl group having from -6 to 12 ring atoms, as defined above, which may contain one or more heteroatoms, more preferably any substitution with a carbon ring atom More preferably an optionally substituted phenyl or naphthyl group, more preferably a phenyl group, wherein the aromatic hydrocarbyl group preferably has 1 to 4, preferably 1 or 2, More preferably substituted by one substituent, each independently selected from linear or branched, saturated or partially unsaturated hydrocarbyl groups as defined above, preferably any of the substituents may be linear or branched (C1 -C50) alkyl group, preferably a linear or branched (C1-C30) alkyl group, more preferably a linear or branched (C1-C20) alkyl group;

Selected; or

(3) = O;

.

The most preferred silanol condensation catalyst (b) of the present invention is a subgroup compound of the formula (Me ^{+ n)} (OCR ¹ ═CH-C (C═O) R ³ ) _m R ⁴ (Ic) Ic is a subgroup (Icc) of a compound of formula (Ic) wherein Me is selected from Ti, Zr, Hf, Cu or Zn, more preferably selected from Ti, Cu or Zn; n, m and s are as defined under the above compound (Ic);

Each R ¹ is independently selected from the group -X _w -R ^{1 '} , wherein X is O or N, more preferably O; w is 0 or 1, preferably 0; The R ¹ 'moiety is selected from linear or branched (C1-C30) alkyl groups, more preferably selected from linear or branched (C1-C20) alkyl groups, more preferably linear or branched , And even more preferably selected from linear or branched (C1-C6) alkyl groups;

Each R ³ is independently selected from the group -X _w -R ^{1 '} , wherein X is O or N, more preferably O; w is 0 or 1, preferably 0; The R ^{1 '} moiety is selected from linear or branched (C1-C30) alkyl groups, more preferably selected from linear or branched (C1-C20) alkyl groups, more preferably linear or branched , And even more preferably selected from linear or branched (C1-C6) alkyl groups; And

Each R ⁴ is independently selected from the group consisting of X _w -R ¹ '

Wherein X is N or O, more preferably O; w is 0 or 1, preferably w is 1; The R ¹ 'moiety

More preferably from a linear or branched (C1-C20) alkyl group, more preferably from a linear or branched (C1-C20) alkyl group, more preferably from a linear or branched From a topographical (C1-C6) alkyl group; or

- linear or branched (C1-C20) alkyl (O- (C1-C20) alkyl) _p, (C1-C20) alkyl (O- (C1-C20) alkenyl) _p or (C1-C20) alkyl, -O (C1-C20) alkyl) _e (C1-C20) alkenyl) _f, wherein each p is independently 1, 2 or 3, each e is independently 0, 1 or 2, and each f is independently 0, 1 or 2; Preferably a linear or branched (C1-C12) alkyl (O- (C1-C12) alkyl) _p or (C1-C12) alkyl (O- (C1-C12) alkenyl) _p, and more preferably linear or branched, (O- (CrC6) alkyl) _p or (CrC6) alkyl (O- (CrC6) alkenyl) _p wherein each p is independently 1 or 2 ;

Selected,

More preferably, the R < ¹ &^gt; moiety is

More preferably a linear or branched (C1-C20) alkyl group, more preferably a linear or branched (C1-C12) alkyl group, more preferably a linear or branched (C1- C6) alkyl group;

Is selected.

The two or more R ⁴ substituents of the compounds (I), (Ia), (Ib), (Ic) or (Icc) defined in the above or the claims may be the same or different. In the case of two or more R < ⁴ > groups, they are most preferably identical.

Two or more (OCR ¹ = CR ² -C (C = O) R ³ ) moieties of compounds (I), (Ia), (Ib), (Ic) or Or may be different. In the case of two or more (OCR ¹ = CR ² -C (C = O) R ³ ) moieties, they are most preferably identical.

The compound (I), (Ia), (Ib), (Ic) or (Icc) of ^{(OCR 1 = CR 2 -C (} C = O) R 3) moiety in the R ¹ and R are defined in the claims or ^{The 3-} substituents may be the same or different. The R ¹ and R ³ substituents are preferably the same.

As non-limiting examples of preferred compounds (Ic) such as compounds (I), the following compounds (Icc) can be mentioned:

Titanium diisopropoxide bis (2,4-pentanedionate) supplied by DuPont, CAS-nr: 17927-72-9,

Copper (II) acetylacetonate supplied by Sigma-Aldrich, CAS-nr: 13395-16-9, and

Zinc acetylacetonate supplied by Sigma-Aldrich, CAS-nr: 108503-47-5.

The most preferred compound (I) is compound (Ic), more preferably (Icc), wherein the metal is titanium (Ti) or copper (Cu).

Suitable compound (I) as the silanol catalytic compound (b) comprising the preferred subgroups is well known and may be commercially available or may be prepared according to processes described in the chemical literature or analogous methods.

The polyolefin (= polyolefin (a)) containing the hydrolyzable silane group (a)

As used herein, the term "polymer" refers to a polyolefin, such as, for example, polyethylene, which refers to a homopolymer or copolymer, such as a homopolymer of an olefin such as a homopolymer and a copolymer ethylene And copolymers.

The hydrolyzable silane group may be prepared by copolymerization of an olefin monomer such as ethylene having a minimum of silane groups including a comonomer or by grafting a silane group containing a polyolefin compound May be introduced into the polyolefin. The grafting is preferably carried out by a radical reaction such as the presence of a radical forming reagent (e.g., peroxide). Both of these techniques are well known in the art.

Preferably, the polyolefin containing the hydrolysable silane group (a) is a copolymer of olefin having a comonomer and optionally a silane group containing another comonomer; Homopolymers or copolymers of olefins having silane groups introduced by grafting of silane groups comprising polyolefin polymer compounds.

As is well known, a comonomer refers to a comonomer unit that can be copolymerized.

The silane group comprising a comonomer for silane group copolymerization or a silane group comprising a compound for silane grafting to prepare polyolefin (a) is preferably a silane group having the formula R ¹ SiR ² _q Y _3- is an unsaturated silane compound / comonomer represented by _q (II)

Wherein R ¹ is an ethylenically unsaturated hydrocarbyl group, a hydrocarbyloxy group or a (meth) acryloxy hydrocarbyl group,

R ² is an aliphatic saturated hydrocarbyl group,

Y, which may be the same or different, is a hydrolyzable organic group and q is 0, 1 or 2.

The hydrocarbyl moiety present in any substituent as R ^{1 in the} compound / comonomer (II) may be a linear or branched hydrocarbyl or cyclic hydrocarbyl. A more preferred compound / subgroup of comonomer (II) is a compound / comonomer of formula (IIa) wherein R ¹ is vinyl, allyl, isopropenyl, butenyl butenyl, cyclohexanyl, or gamma- (meth) acryloxy alkyl; Y is methoxy, ethoxy, formyloxy, acetoxy, propionyloxy or an alkyl- or arylamino group, and R ^2, if present, is methyl (methyl), ethyl (ethyl), propyl (propyl), decyl (decyl) or phenyl (phenyl) group, preferably R ² is not present.

Even more preferred subgroups of silane compounds (II) are compounds / comonomers selected from compounds of formula (IIc) / comonomers or compounds of formula (IId) / comonomers:

CH ₂ = CH- (CH ₂ ) _t -Si (OA) ₃ (IIc),

Wherein t is 0 to 6, preferably 0 to 5, preferably 0 to 4, more preferably 0 to 3, preferably 0 to 2, most preferably 0;

A is a hydrocarbyl group, formyl group or acetyl group, preferably a hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms; or

???????? CH ₂ = C (X) -C (═O) -O- (CH ₂ ) _s -Si (OA) ₃ (IId)

Where s is 1 to 6, preferably 1 to 5, more preferably 1 to 4, more preferably 1, 2 or 3, most preferably 3;

X is H or CH _3, preferably CH _3; And

A is a hydrocarbyl group, formyl group or acetyl group, preferably a hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

As will be apparent to those skilled in the art, the choice of a suitable unsaturated silane compound / comonomer will depend on the desired cross-linking effect, such as, for example, the desired cross-linking rate at which the preferred accessibility of the cross-linking catalyst silane groups can be adjusted. As is well known, the accessibility can be adjusted in turn by, for example, the length of the side chain protrusion from the polymer backbone.

The most preferred compound is compound (IIc), preferably vinyl trimethoxysilane, vinyl bismethoxyethoxysilane, or vinyl triethoxysilane.

Suitable silane groups comprising comonomers for silane group copolymerization or silane groups comprising compounds for silane grafting to prepare polyolefin (a) are well known and may be commercially available, for example, or as described in the chemical literature Or similar methods.

Suitable polyolefins for polyolefins containing hydrolyzable silane groups (a) may be any polyolefin, such as any of the conventional polyolefins, which can be used to produce the product of the invention, preferably a cable layer of cable. Suitable conventional polyolefins, for example, are well known and may be commercially available, for example, or may be prepared according to a polymerization process or similar process as described in the chemical literature.

The polyolefin (a) for the polymer composition is preferably selected from polypropylene (PP) or polyethylene (PE) containing hydrolyzable silane groups, preferably polyethylene.

When the polyolefin (a) is a polymer of ethylene having at least one comonomer other than the silane group containing comonomer (briefly another comonomer in this specification), the silane group may be selected from the group consisting of a silane group containing a compound / grafting, or copolymerization, and other suitable comonomers are selected from non-polar comonomers or polar comonomers, or mixtures thereof. Other preferred non-polar comonomers and polar comonomers are described in the context of polyethylene produced through the following high pressure process.

Preferred polyolefins (a) are polyethylene produced in the presence of an olefin polymerization catalyst or polyethylene produced through high pressure fixation, which contain hydrolyzable silane groups.

"Olefin polymerization catalyst" means herein preferably a coordination catalyst. Such coordination catalysts are well known in their meaning and preferably include Ziegler-Natta catalysts and metallocene and non-methylene catalysts, or chromium (chromium) catalysts, or mixtures thereof. Is selected from a single site catalyst. The meaning of the word is well known.

Polyethylenes polymerized in the presence of an olefin polymerization catalyst are also often referred to as low pressure polyethylene in order to distinguish clearly from polyethylene produced in a high pressure process. Both expressions are well known in the polyolefin field. The low pressure polyethylene may be prepared in a polymerization process operating in bulk, slurry, solution, or gas phase conditions, or combinations thereof. The olefin polymerization catalyst is typically a coordination catalyst.

More preferably, the polyolefin (a) is selected from homopolymers or copolymers of ethylene containing hydrolyzable silane groups, prepared in the presence of a coordination catalyst or prepared via a high pressure polymerization process.

In the first embodiment of the polyolefin (a) of the polymer composition of the present invention, the polyolefin (a) is low pressure polyethylene (PE) containing a hydrolyzable silane group. The low pressure polyethylene is preferably selected from very low density ethylene copolymers (VLDPE), linear low density ethylene copolymers (LLDPE), medium density ethylene copolymers (MDPE) or high density ethylene homopolymers or copolymers (HDPE). These well-known species are named according to their density regions. The term VLDPE includes polyethylene known herein as plasto and elastomer and covers a density range of 850 to 909 kg / m < ^{3 &} gt ;. The LLDPE has a density of greater than 909 and less than 930 kg / m ³ , preferably greater than 909 and less than 929 kg / m ³ . MDPE has a density greater than a density of less than 929 945 kg / m ^3, preferably 930 to 945 kg / m ^3. HDPE has a density of density, preferably 946 kg / m ^3, preferably 946 to 977 kg / m ^3, more preferably 946 to 965 kg / m ³ greater than 945 kg / m ^3. More preferably, the low pressure copolymer of ethylene for said polyolefin (a) is a C3-20 alpha olefin, more preferably a C4-12 alpha-olefin, more preferably a C4-8 alpha-olefin such as 1-butene, 1-pentene, 1-hexene, 1-octene, or mixtures thereof. The amount of comonomer present in the PE copolymer is from 0.1 to 15 mol%, and typically from 0.25 to 10 mol%.

In addition, when the polyolefin (a) is a low pressure polyethylene polymer containing hydrolyzable silane groups, the polyethylene may be unimodal or multimodal in terms of molecular weight distribution (MWD = Mw / Mn). In general, polymers comprising two or more polymer fractions, prepared under different polymerization conditions and having different molecular weights (average weight) and molecular weight distribution, are referred to as multimodal. The prefix multi refers to the number of different polymer fractions present in the polymer. Thus, for example, multimodal polymers include so-called bimodal polymers of two fractions.

Polymer conditions refer to one of the process variables, feeds and catalyst systems herein.

Unimodal low pressure polyethylene can be produced by a single polymerization step in a single reactor in a well known and documented manner. The multimodal polyethylene may be prepared in a polymerization reactor by varying the polymerization conditions and any catalyst, or, preferably, in a multistep polymerization process comprising two or more successive polymerization zones. The polymerization zones are connected in parallel, and preferably the polymerization zones operate in a cascaded mode. In a preferred multistage process, the first polymerization stage is carried out in a slurry reactor such as one or more loops, and the second polymerization stage is carried out in one or more gas phase reactors. One preferred multistage process is disclosed in EP517868. Preferably, the same catalyst is used in each polymerization step of the multi-step process.

LLDPE, MDPE or HDPE as defined above or below is a preferred type of polyethylene, more preferably LLDPE copolymer, for the polyolefin (a) as defined above or below. Such LLDPE may be unimodal or multimodal.

The silane groups comprising the units are introduced into the low pressure polyethylene by grafting or copolymerization of ethylene with a silane group comprising comonomers and optionally other comonomers which are preferably nonpolar comonomers. Hydrolyzable silane groups containing low pressure polyethylene as the preferred polyolefin (a) are HDPE homopolymers or copolymers, MDPE copolymers or LLDPE copolymers wherein the silane groups are introduced by grafting of the silane groups comprising the compound. As the polyolefin containing the hydrolyzable silane group, the low pressure polyethylene preferably has a melt viscosity of up to 1200 g / 10 min, preferably up to 500 g / 10 min, preferably up to 400 g / 10 min, Preferably up to 300 g / 10 min, preferably up to 200 g / 10 min, preferably up to 150 g / 10 min, preferably from 0.01 to 100, preferably from 0.01 to 50 g / 10 min, Has a MFR ₂ of 0.01 to 40.0 g / 10 min, preferably 0.05 to 30.0 g / 10 min, preferably 0.1 to 20.0 g / 10 min, more preferably 0.2 to 15.0 g / 10 min.

In the second embodiment of the polyolefin (a) of the present invention, the polyolefin (a) is a polyethylene produced by high pressure polymerization (HP) and contains a hydrolyzable silane group. In this embodiment, the polyethylene is preferably low pressure polyethylene (LDPE) which is prepared in the presence of an initiator and more preferably contains hydrolyzable silane groups. It should be noted that the polyethene produced in the high pressure (HP) process is generally referred to herein as LDPE and the word has a well-known meaning in the polymer art. Although LDPE is an abbreviation for low density polyethylene, the word is not meant to limit the range of density, but is understood to include low density, medium density and high density polyethylene such as HPPET from LDPE. The term LDPE describes and distinguishes only the properties of HP polyethylene having typical characteristics, such as different branch structures, as compared to the polyethylene (PE) produced in the presence of an olefin polymerization catalyst.

A preferred embodiment is the second embodiment, wherein the polyolefin (a) is a polyethylene prepared by a high pressure (HP) process and containing a hydrolyzable silane group. In this second preferred embodiment, the hydrolyzable silane group containing the LDPE polymer as the polyolefin (a) is a low density homopolymer of ethylene (referred to herein as LDPE homopolymer) or a low density copolymer of ethylene with one or more other comonomers (Hereinafter referred to as an LDPE copolymer), wherein the hydrolyzable silane group containing the compound is introduced into the above-mentioned LDPE polymer or comprises a comonomer as defined above and optionally one or more other comonomers (Hereinafter referred to as LDEP copolymer) of ethylene having at least one silane group. The one or more other comonomers of the LDPE polymers are preferably selected from mixtures of polar comonomers, non-polar comonomers or polar comonomers and non-polar comonomers, as defined above or below. Also, the LDPE homopolymer or LDPE copolymer referred to as polyolefin (a) is optionally unsaturated.

If polar comonomers for LDPE copolymers containing hydrolysable silane groups as the preferred polyolefin (a) are present, the polar comonomers are preferably selected from the group consisting of hydroxyl, alkoxy, carbonyl, carboxyl, ether or ester groups, ≪ / RTI > In addition, comonomers containing carboxyl and / or ester groups are more preferred as the polar comonomers. Even more preferably, the polar comonomers of the hydrolysable silane groups containing LDEP copolymers, if present, are selected from the group of acrylates, methacrylates or acetates or any mixture thereof. If present in the hydrolyzable silane group containing the LDEP copolymer, the polar comonomer is preferably selected from alkyl acrylates, alkyl methacrylates or vinyl acetates, or mixtures thereof, more preferably C1 to C6-alkyl acrylates, C1 to C6-alkyl methacrylate or vinyl acetate. Even more preferably, if a polar comonomer is present, the hydrolyzable silane group containing the LDEP copolymer can be a C ₁ - to C ₄ -alkyl acrylate such as methyl, ethyl, propyl or butyl acrylate containing hydrolysable silane groups Is a copolymer of ethylene.

If there is a non-polar comonomer for the LDPE copolymer containing a hydrolyzable silane group as the preferred polyolefin (a), comonomers other than the polar concomers defined above may be used. Preferably, the non-polar comonomers exclude comonomers comprising a hydroxyl group, an alkoxy group, a carbonyl group, a carboxyl group, an ether group or an ester group. One group of preferred non-polar comonomers is a monounsaturated (= double bond) comonomer, preferably olefins, preferably alpha-olefins, more preferably propylene, 1-butene (1- butene, 1-hexene, 4-methyl-1-pentene, styrene, 1-octene, C ₃ to C ₁₀ alpha-olefins such as polyunsaturated (e.g., one or more double bonds such as diene) comonomers; Or any mixture thereof, and preferably consists of these.

If the LDPE polymer containing the hydrolyzable silane group as the preferred polyolefin (a) is a copolymer of ethylene with other comonomers, the amount of other comonomers present in the LDPE polymer is preferably 0.001 to 50 wt-%, more preferably 0.05 To 40% by weight, still more preferably 35% by weight or less, still more preferably 30% by weight or less, still more preferably 25% by weight or less.

As already mentioned, like the preferred polyolefin (a) by grafting or copolymerization of ethylene with a silane group containing a comonomer and any other comonomer, the silane group is a high pressure polyethylene, preferably an LDPE polymer Can be introduced. In this second preferred embodiment, the polyolefin (a) is an HP polyethylene containing hydrolyzable silane groups, most preferably an LDEP aerial of ethylene having a silane group and other comonomers comprising comonomers as defined above or below It is united.

Typically, and preferably for wire and cable (W & C) applications, the density of LDPE polymers containing hydrolysable silane groups as polyolefin (a) is higher than 860 kg / m ³ . Preferably, the density of the LDPE polymer is not higher than 960 kg / m ³ , preferably 900 to 945 kg / m ³ . The MFR ₂ (2.16 kg, 190C) of the LDPE polymer containing the hydrolyzable silane group as the polyolefin (a) is preferably 0.01 to 50 g / 10 min, more preferably 0.01 to 40.0 g / 10, 10 min, and most preferably from 0.2 to 10 g / 10 min.

Thus, LDEP polymers for polyolefin (a) are preferably prepared by free radical initiated polymerization at high pressure (indicating high pressure (HP) radical polymerization). The HP reactor can be a well known tubular or autoclave reactor or a mixture thereof, and is preferably a tube reactor. Control of process conditions to adjust other properties of the polyolefin depending on high pressure (HP) polymerization and the desired final application is well known and well described in the literature and can be readily utilized by those skilled in the art. A suitable polymerization temperature range is up to 400 DEG C, preferably 80 to 350 DEG C, and the pressure is from 70 Mpa, preferably 100 to 400 Mpa, more preferably 100 to 350 MPa. The pressure can be measured at least after the compression step and / or after the tube reactor. The temperature can be measured at various points in all stages.

For more information on the preparation of ethylene (co) polymers by high pressure radical polymerization, see Encyclopedia of Polymer Science and Engineering, Vol. 6 (1986), pp 383-410 and Encyclopedia of Materials: Science and Technology, 2001 Elsevier Science Ltd.: Polyethylene: High-pressure, R. Klimesch, D.Littmann and F.-O. Mhling pp. 7181-7184.

The polyolefin (a) containing a hydrolysable silane group is most preferably a homopolymer or a copolymer of ethylene grafted with a silane group prepared in a low pressure polymerization process in the presence of a coordination catalyst as defined above or containing a compound as defined above From an ethylene copolymer prepared in a high pressure polymerization process, as defined above or below, by ethylene copolymerization with one or more silane groups containing a comonomer as defined above or below and optionally one or more other comonomers Is selected. More preferably, the polyolefin containing hydrolyzable silane groups (a) is obtained by copolymerization of ethylene in a high pressure process with a minimum of silane groups containing comonomers as defined above and one or more other comonomers.

Polymer composition (= polymer composition of the present invention)

The polymer composition is preferably present in an amount of from 0.001% by weight or more, preferably up to 6.0% by weight, preferably from 0.01 to 2.0% by weight, based on the total amount of the polyolefin (a) and the silanol condensation catalyst compound of formula (I) More preferably 0.02 to 0.5% by weight of the silanol condensation catalyst compound of formula (I).

The polymer composition preferably comprises 99.9999% by weight or less, preferably at least 94.0% by weight or more of the polyolefin (a), preferably at least 95.0% by weight, based on the total amount of the polyolefin (a) and the silanol condensation catalyst compound of formula (I) Preferably 99.99 to 98.0% by weight, more preferably 99.98 to 99.5% by weight.

Preferably, the polymer composition comprises a hydrolyzable silane group in an amount of 0.001 to 12 mol%, preferably 0.01 to 4 mol%, most preferably 0.05 to 1.6 mol%, based on the total amount (weight) of the polymer composition. More preferably, the molar percent amount of the hydrolyzable silane groups (calculated from the wt% determined under "Determination Method") is based on the total amount of the polyolefin (a) component.

"Silane group" means a hydrolyzable silane moiety herein. The preferred silane-moiety is the (Y) _3- qSi-moiety as defined in the above formula (II), as is known in the art, between the other hydrolysable silane groups present in the polyolefin (a) Can be cross-linked by hydrolysis and subsequent condensation reaction in the presence of a silanol condensation catalyst and water to form Si-O-Si. Preferred hydrolyzable silane groups are hydrolyzable (AO) ₃ Si-moieties as defined in formula (IIc) or (IId) above.

The polymer composition may further comprise such additional polymer components as a blendable thermoplastic resin, additive, an additional stabilizer such as an antioxidant, a water-dendritic retarder, a scorch retarder; Lubricants such as carbon black, foaming agents, fillers; Or a dye.

The total amount of additional polymer components, if present, is typically up to 60% by weight, preferably up to 50% by weight, preferably up to 40% by weight, more preferably 0.5 to 30% by weight, To 25% by weight, more preferably 1.0 to 20% by weight.

The total amount of additives, if present, is generally from 0.01 to 10% by weight, preferably from 0.05 to 7% by weight, more preferably from 0.2 to 5% by weight, based on the total amount of the polymer composition.

The polymer composition may, and preferably comprises, an antioxidant. Preferably the antioxidant is present in the composition in an amount of 0.01 to 3% by weight, more preferably 0.05 to 2% by weight, most preferably 0.08 to 1.5% by weight, based on the total amount of the polymer composition.

If the polymer composition is used as a semiconductor composition, a filler such as a conductive filler such as conductive carbon black; Or a flame retardant filler such as magnesium hydroxide or aluminum hydroxide if used as a flame retardant composition; Ultraviolet protective fillers such as ultraviolet carbon black or ultraviolet stabilizers, if used as an ultraviolet stabilizing composition; Or any combination thereof. As will be apparent to those skilled in the art, the amount of the filler generally depends on the nature of the filler and the desired final application. For example, where the polymer composition comprises a conductive filler, the amount is up to 65% by weight, preferably 5 to 50% by weight, based on the total amount of the polymer composition.

The polymer composition may typically include a dye that may be added to the composition in the form of a color masterbatch. Such color masterbatches may be commercially available or may be manufactured in a conventional manner by combination of a carrier medium and a dye. The amount of dye masterbatch, if present, is preferably up to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of polymer composition.

The catalyst (b) may be added to the polyolefin (a) as a neat (i.e., provided by the supplier) or in the master batch (MB). In the case of MB, the carrier medium may be a liquid or solid such as, for example, a carrier polymer.

The amount of polyolefin (a) in the polymer composition of the present invention is typically at least 35 wt%, preferably at least 40 wt%, preferably at least 50 wt%, preferably at least 75 wt%, based on the total amount of polymer components present in the polymer composition By weight, more preferably 80 to 100% by weight, and still more preferably 85 to 100% by weight. The preferred polymer composition consists of the polyolefin (a), which is the only polymer component. This expression means that the polymer composition does not contain additional polymer components and contains the polyolefin (a) as the only polymer component. However, it is understood that this may include other components than the polyolefin (a), such as an additive that can be selectively added to the mixture with the carrier polymer, referred to herein as the so-called masterbatch. The catalyst (b) can also be added to the form of the master medium, wherein the carrier medium is a polymer. In this case, the carrier polymer of the masterbatch is not calculated as the amount of the polymer component but is calculated as the total amount of the polymer composition.

The polymer compositions of the present invention can be prepared prior to or subsequent to the production of an article, preferably a cable.

In a first embodiment for the preparation of the polymer composition, the polyolefin (a) and the catalyst (b) are preferably bonded together prior to the formation of a product having a layer of one or more cables. The catalyst (b) may be added in the form of MB or added to the polyolefin (a) in the same manner as the solid catalyst (b). The components are preferably combined with one another by manufacturing in conventional manner, such as extruding the components into a screw extruder or kneader. The melt mixture obtained as described above is preferably pelletized and the pellets of the polymer composition, which can be of any size and shape, can be used in the production process of products which are preferably cables. Otherwise, in this first embodiment for preparing a polymer composition, the addition of a portion of the other component, such as preparation of the polymer composition or catalyst (b) or additive, or any mixture thereof, Or in a mixer prior to a cable extruder, or in a cable extruder, or both. The mixture thus obtained is preferably used to form a product which is one or more cable layers.

In a second embodiment, the catalyst (b) is combined with the polyolefin (a) after formation of the product, preferably a cable, from the polyolefin (a). For example, the catalyst (b) can migrate from the other layer adjacent to the layer to the cable layer of the polyolefin (a) and the polymer composition can be formed after the layer is formed, for example, prior to cross- do.

The first or second embodiment for preparing the polymer composition can be selected according to the desired product, which is preferably a preferred cable application of the polymer composition.

Final use of polymer compositions

The present invention also provides an article comprising a polymer composition comprising a polyolefin (a) and a catalyst (b) as defined above or below.

The preferred product is a power cable, more preferably an LV, MV or HV cable, which is a hydrocracking silane group (a) and a silanol condensation catalyst compound of formula (I) as defined above or below and b) at least one layer of a polymeric composition comprising, preferably, the polymeric composition.

The preferred power cable

- a cable (A) comprising a conductor surrounded by at least one layer of insulation, preferably comprising a polymer composition comprising a polyolefin (a) as defined above or in the claims and a catalyst composition of component (I) ; or

Preferably one or more layers, preferably one or more layers of an insulator, comprising a polymer composition comprising the polyolefin (a) and the catalyst compound (b) of formula (I) (B) comprising a conductor surrounded by a layer, an insulator layer and an outer semiconductor layer.

The cable A is preferably an LV or MV cable. The cable (B) is preferably an MV cable or an HV cable.

In the embodiment of cable (B), the first and second semiconductor compositions may be different or the same and preferably comprise a polymer which is a mixture of polyolefin or polyolefin and conductor filler, preferably carbon black. In the case of cable (B), one or both, and preferably both, of the insulator layer and, optionally and preferably, the inner semiconductor layer and the outer semiconductor layer comprise the polymer composition of the present invention. In this case, the polyolefin (a) of the polymer composition and / or the catalyst compound (b) of the formula (I) may be the same or different.

The above or below conductors herein means that the conductor comprises one or more wires. The cable may also include one or more such conductors. Preferably the conductor is an electrical conductor and comprises at least one metal wire.

In a preferred cable of the present invention at least the insulator layer comprises a polymer composition.

The insulation layer for medium or high voltage power cables typically has a thickness of at least 2 mm, typically at least 2.3 mm, which increases as the voltage of the designed cable increases.

As is well known, the cable may optionally include an additional layer such as a layer surrounding the insulator layer, or an external semiconductor layer, if present, such as a screen, sheath layer, another protective layer, or any combination thereof.

The polymer compositions of the present invention are preferably cross-linked.

Thus, the polymer compositions of the present invention are preferably cross-linkable. Cross-linkability means that the polymer composition can be cross-linked using the catalyst compound (b) of formula (I) before use of the final application thereof. In addition, the article of manufacture, preferably a cable, is cross-linkable and cross-linked prior to its final use.

Thus, the product preferably being a cable of the present invention is preferably cross-linkable. There is preferably provided a cross-linked product comprising the polymer composition as defined above or as defined in the claims, which is cross-linked in the presence of catalyst (b) or as defined in the claims. More preferably, there is provided a cross-coupled cable comprising a conductor surrounded by at least one layer, preferably at least one insulator layer, wherein said at least one layer, preferably one or more insulator layers, Comprises, preferably, a polymer composition as defined above or in the claims, cross-linked in the presence of catalyst (b). The cross-linked cable is novel because it comprises a layer of a polymer composition comprising the moiety of the catalyst (b).

The present invention also provides a method of making a product comprising the steps of forming a product using a polymer composition as defined above or below.

A preferred process is a process for producing a cable according to the invention, as defined above, wherein the process is preferably carried out by (co) extrusion,

(a) a polyolefin containing a hydrolyzable silane group and

(b) applying to the conductor one or more layers, preferably comprising the polymer composition, comprising a polymer composition comprising a silanol condensation catalyst compound of formula (I) as defined above or below in the claims do.

As used herein, (co) extrusion means that, in the case of two or more layers, the layers may be extruded in separate steps, or two or more of them may be co-extruded in the same extrusion step . (Co) extrusion herein also means that all or part of the layer is formed simultaneously using one or more extruder heads. For example, triple extrusion can be used to form three layers. If the layer is formed using one or more extrusion heads, for example, the layer may comprise a first head for the formation of the inner semiconductor layer and an inner portion of the insulator layer, an outer insulator layer and a second Layer, it can be extruded using two extrusion heads. (Co) extrusion can be performed in any existing cable extruder, such as a single or twin screw extruder.

As is well known, the meltmix of the polymer composition or its component is applied to form a layer. Meltmixing refers to mixing of the resulting mixture above the melting point of at least the main polymer component and is carried out, for example, without limitation, at a temperature of the melting point or softening point of the polymer component of at least 15 캜. The melt mixing may be carried out in a cable extruder or in a mixer such as a kneader prior to the extruder, or both.

A more preferred cable manufacturing method is

(i) a polymeric composition comprising a polyolefin (a) and a catalyst compound of (b) of compound (I) as defined above or below, preferably by (co) Applying at least one insulator layer to the conductor, wherein the cable (A), or

(ii) a polymer composition comprising the polyolefin (a) and the (b) catalyst compound of the polyolefin (a) and the compound (I) as defined above or below, preferably by (co) extrusion Applying an outer semiconductor layer comprising an inner semiconductor layer comprising a first semiconductor composition, an insulator layer comprising an insulator composition and a second semiconductor layer, wherein at least one layer of the composition, preferably at least an insulator composition of the insulator layer, (B) according to the manufacturing method.

In this embodiment of cable (B), the first and second semiconductor compositions may be different or the same and preferably comprise a polymer which is a mixture of polyolefins or polyolefins and preferably a conductive filler which is carbon black.

As is well known, the polymer composition of the layer of cable can be prepared before or during the cable manufacturing process. The polymer composition of the layer also includes some or all of the components of the final composition before being independently introduced into the (melt) mixing step a) of the cable manufacturing process. The remaining components are then introduced during or after the formation.

At least in the preferred cable the insulator layer comprises, and preferably consists of, a polymer composition. In this example, the polyolefin (a) and the compound of formula (I) of the polymer composition are prepared according to the first embodiment of the preparation process of the polymer composition described above, before the polymer composition is introduced into the cable production line in the form of the desired pellets .

When one or both of the semiconductor layers of the cable (B) comprises, and preferably consists of, a polymer composition, the polymer composition preferably comprises a polyolefin (a) According to the second embodiment of FIG. The catalyst compound (b) of formula (I) can then be moved to form a semiconductor layer from another layer, which is typically an insulator layer.

The product manufacturing process of the present invention preferably includes the additional step of cross-linking the manufactured product. According to a preferred embodiment of the process, a cross-linked cable is prepared, wherein the process comprises the additional step of cross-linking to obtain at least one layer comprising the polymer composition as defined in the or the following claims.

The cross-linking is carried out in the presence of (b) the catalyst compound of formula (I) and water, which is referred to as moisture curing. Water may be in the form of a liquid or vapor, or a combination thereof. The silane groups present in the polyolefin (a) undergo hydrolysis under the influence of water in the presence of the present (b) silanol condensation catalyst compound of formula (I), so that the alcohol is separated and a silanol group is formed, Wherein the water is separated and a Si-O-Si linkage is formed between the hydrolyzed silane groups present in said polyolefin (a). The cross-linked polymer composition has a typical network that is an interpolymer bridge, as is well known in the art. In general, moisture curing is carried out in so-called saunas or water baths at ambient conditions or temperatures of 70 to 100 캜.

The process for the preparation of the product is also preferably carried out in the presence of a catalyst compound (b) of formula (I) and water as defined above or below,

(i) cross-linking the insulator composition of the insulator layer of cable (A) in the presence of the catalyst compound (b) and water of formula (I) as defined above or in the claims below, or

(ii) an insulating composition of at least one insulator layer, a cross-linking of the first semiconductor composition of the inner semiconductor layer of the cable (B) or the second semiconductor composition of the outer semiconductor layer,

Preferably cross-linking at least in the insulator composition of the insulator layer,

Cross-linking of the insulator composition of the insulator layer and cross-linking of the first semiconductor composition of the at least one inner semiconductor layer and of the second semiconductor composition of the outer semiconductor layer,

Bonding the insulating composition of the insulator layer, the first semiconductor composition of the inner semiconductor layer, and, optionally, the second semiconductor composition of the outer semiconductor layer, more preferably.

In the case of cable B, the outer semiconductor layer may be bonded (non-peelable) or peelable, and the word has well-known meaning. The bonded outer semiconductor layers are typically cross-coupled. The peelable outer semiconductor layer is typically not cross-linked.

Thus, in the case of the cable B, preferably, the inner semiconductor layer, the insulating layer and the outer semiconductor layer are crosslinked as they are bonded or peeled.

A cross-linked cable obtainable by the above manufacturing method is also provided.

Provides for the use for crosslinking one or more layers of a cable comprising the polyolefin (a) as defined above or below.

Determination methods

% By weight: % by weight

The total amount means the weight, and in the case of 100%, 100% by weight. For example, the total amount of the polymer composition (100% by weight).

Melt flow rate

The melt flow rate (MFR) is determined according to ISO 1133 and is expressed in g / 10 min. The MFR is an index of the fluidity of the polymer and is therefore processable. Higher melt flow rate of polymer, lower viscosity. The MFR is measured at 190 C for polyethylene. The MFR can be measured at different loads such as 2.16 kg (MFR ₂ ) or 21.6 kg (MFR ₂₁ ).

density

Low Density Polyethylene (LEPE): Density was measured according to ISO 1183-2.

The preparation of the specimens was carried out according to ISO 1872-2 Table 3 Q (compression molding).

Low process polyethylene: The density of the polymer was measured according to ISO 1183 / 1872-2B.

Gel content

The tape specimens prepared under the preparation of the tape samples in the following experimental part were measured with two deviations from this standard using decaline extraction according to ASTM D 2765-01, Method B, with the following two deviations:

1) Additional extraction for one hour with fresh decalin was done to extract soluble material.

2) Only 0.05% of the antioxidant (Irganox 1076) was added to decalin instead of 1% as described in the standard.

The gel content was calculated according to ASTM D 2765-01.

Hot set elongation test

The tape samples prepared under preparation of the tape samples in the following experimental part are used to measure the properties of the hot set. Three dumb-bells samples removed along the extrusion direction were prepared according to ISO 527 5A from a cross-bonded tape of thickness 1,7 + -0,1 mm. The hot set test is made according to EN 60811-2-1 (hot set test) by thermal deformation measurement.

The baseline was marked 20mm above the dumbbell. Each test sample was fixed vertically from the top end in an oven and a load of 0.1 MPa was attached further below each test sample. After 15 minutes, the distance between pre-marked lines in an oven at 200 ° C was measured and the percentage of hot set growth,% growth, was calculated. For% permanent set, the tension (weight) was removed from the test sample and cooled to ambient temperature at room temperature after 5 minutes recovery at 200C. Percent permanent strain was calculated between the indicated lines. Averages of three tests were reported.

The content of polar comonomers (wt% and mol%): The comonomer content (wt%) of the polar comonomer is

Haslam J, Willis HA, Squirrel DC. Is measured in a a ¹³ C-NMR as described in the 1972 calibrated (calibrate) a known manner based on Fourier transform infrared spectroscopy measurement (FTIR, Fourier transform infrared spectroscopy) ; Identification and analysis of plastics, 2 nd ed.LondonIliffebooks. The FTIR instrument is a Perkin Elmer 2000, 1scann, resolution 4 cm ^-1 .

For the measurement of comonomers, a film with a thickness of 0.1 mm was prepared. The peak for the used conomer is compared to the peak of the polyethylene as is apparent to those skilled in the art (for example, the peak of butyl acrylate at 3450 cm ^-1 was compared to the peak of polyethylene at 2020 cm ^-1 ). The weight-% was converted to mol-% by calculation based on the total number of moles of polymerizable monomers.

For the measurement of comonomers, a film with a thickness of 0.1 mm was prepared. The peak for the used conomer is compared to the peak of the polyethylene as is apparent to those skilled in the art (for example, the peak of butyl acrylate at 3450 cm ^-1 was compared to the peak of polyethylene at 2020 cm ^-1 ). The weight-% was converted to mol-% by calculation based on the total number of moles of polymerizable monomers.

Content (mol-%) of hydrolyzable silane group (Si (Y) _3-q ) using fluorescent X-ray analysis : The pellet sample was pressed with a 3 mm thick flake (150 ° C for 2 min, Lt; / RTI > The Si (silicon) - atom content was analyzed by wavelength dispersive XRF (AXS S4 Pioneer Sequential X-ray Spectrometer supplied by Bruker). The pellet sample was pressed with a 3 mm thick flake (cooled at room temperature after applying pressure of 5 bar for 2 minutes at 150C).

Generally, in an XRF-method, a sample is radioactively treated with an electromagnetic wave having a wavelength of 0.01 to 10 nm. The elements present in the sample will emit fluorescence X-ray radiation along with the characteristic discrete energy of each element. By measuring the intensity of the emitted energy, quantitative analysis can be performed. The quantitative method is to calibrate with a compound having a known concentration of the element of interest, for example, as prepared in a Brabender compounder.

The XRF results show the total content (% by weight) of silicon (Si) and are calculated and expressed here as the mol% - content of the hydrolyzable silane group Si (Y) _3-q .

Experiment Department

Preparation of Experimental Example

The basic polyolefin (a)

Polyolefin I:

The VTMS content of a copolymer of ethylene with a commercially available vinyl trimethoxy silane (VTMS) comonomer, LE4423, supplier Borealis, was 1.35 wt% (0.26 Mol%), a MFR of 1.0 g / 10 min (190 DEG C / 2.16 kg) and a density of 923 kg / m3 produced by high pressure copolymerization in a tubular reactor.

Based master batch (Reference Master Batch):

A silane condensation catalyst, LE4476, is commercially available, wherein the active catalyst component is based on sulfonic acid and is supplied by Borealis.

Inventive Master Batches of the present invention:

Catalyst 1 of the present invention: Titanium diisopropoxide bis (2,4-pentanedionate) CAS-nr: 17927-diisopropoxide bis (2,4-pentanedionate) supplied by DuPont 72-9

Catalyst 2 of the present invention: Copper (II) acetylacetonate CAS-nr: 13395-16-9 supplied by Sigma-Aldrich

Catalyst 3 of the present invention: Zinc acetylacetonate CAS-nr: 108503-47-5 supplied by Sigma-Aldrich

Preparation of the master batch of the present invention:

Three test master batches are prepared. The master batch 1 of the present invention and the master batch 2 of the present invention each contain the same conventional ethylene butyl acrylate copolymer used for the catalyst 1 of the present invention and the catalyst 2 of the present invention and the reference MB Wt.%). The master batch 1 of the present invention thus obtained contains 1.9 wt% of the catalyst 1 of the present invention, and the master batch 2 of the present invention thus obtained contains 1.2 wt% of the catalyst 2 of the present invention.

Prepare a tape sample:

The tape samples were prepared by mixing the polyolefin I with the masterbatch 1 of the present invention or the masterbatch 2 of the present invention and the reference masterbatch using a conventional extruder (Collin Teach-Line Extruder, Type: E 20 T SCD 15, Conditions), to obtain a test polymer composition comprising 2.3 mmol / kg catalyst and 6.9 mmol / kg catalyst, respectively, as given in the table below.

[Table 2] Mixing conditions

The resulting tape samples (with a thickness of 1.8 +/- 0.1 mm) are used for cross-linking and are used for measuring gel content and hot set.

The resulting tape samples were subjected to cross-linking by being maintained under the conditions in a water bath at 90 DEG C as specified in the table below. Thus, hot set elongation was performed after crosslinking for 24 hours in a water bath at 90 DEG C Respectively.

The components of the present invention and their amounts, reference composition, cross-linking conditions, and duration are shown in Tables 3 and 4.

[Table 3] Catalytic effects of compositions 1 and 2 of the present invention as compared to reference composition 1

1. Cross-linking within a water bath at < RTI ID = 0.0 > 90 C &

[Table 4] Catalytic effects of compositions 1 and 2 of the present invention as compared to reference composition 1

1. Cross-linking within a water bath at < RTI ID = 0.0 > 90 C &

2. The measured hot set is the hot set elongation,

Claims (21)

A cable comprising a conductor surrounded by at least one layer comprising a polymer composition, said composition comprising:
(a) an LDPE homopolymer or copolymer containing a hydrolyzable silane group having a density of 900 to 945 kg / m < ³ >, or a LLDPE copolymer, MDPE copolymer or HDPE homopolymer or copolymer containing hydrolysable silane groups, The degradable silane group is derived from the following compounds;
CH ₂ = CH- (CH ₂ ) _t -Si (OA) ₃ (IIc),
Where t is from 0 to 6;
A is a hydrocarbyl group, formyl group or acetyl group; And
(b) a silanol condensation catalyst compound of formula (I);
Me ^{+ n} (OCR ¹ = CR ² - (C = O) R ³ ) _m R ⁴ _s (I),
here,
Me is a metal selected from Groups 4 to 6 and Groups 3 to 12 of the Periodic Table (according to Inorganic Chemistry 1989 IUPAC nomenclature);
n is an integer from 2 to 4;
m is 1 to 3;
s is an integer from 0 to 3;
m + s = n;
Each R ¹ is independently H or R ^{1 'and;}
R ^{1 '} is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S; Or a substituted or unsubstituted aromatic hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S;
Each R < ² > is independently H or R &^lt; ^{1 &} gt ;; or
Each R < ³ > is independently H or R < ¹ &
Each R ⁴ is independently O _w -R ^{1 "} , wherein w is 0 or 1;
R ^{1 "} is a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally containing one or more heteroatoms selected from N, O, P or S, or one or more heteroatoms selected from N, O, A substituted or unsubstituted aromatic hydrocarbyl group optionally containing an atom;
The hydrolysable group for Broensted acid is selected from -Y-R2; Wherein Y is -OC (= O) -, -C (= O) -OC (= O) -, -NR 5 C (= O) -, -OC (= O) NR 5 -, -OC (= O ^{) O-, -NR 5 C (=} O) OR-, -C (= O) NC (= O) -, -OS (= O) 2 -, -OP (= O) 2 -, -NR 5 S _{(= O) 2 -, -OS} (= O) 2 NR 5 -, -SC (= O) -, -OPR 6 (= O) O-, -OP (= O) (oR 6) O-, or -OPR ⁶ (= O) OP (= O) (OR 2) O-, wherein each R ⁵ is independently H or a linear hydrocarbyl group; Each R < ⁶ > is independently H or R2 as defined below; Each R2 is independently a substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S; Or a substituted or unsubstituted aromatic hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S; - = O; Or chlorine (Cl).
The process of claim 1, wherein the silanol condensation catalyst compound (b) is a subgroup of a compound of formula (I), which is a compound of formula (Ic)
Me ^{+ n} (OCR ¹ = CH-C (C = O) R ³ ) _m R ⁴ _s (Ic)
Where Me is a metal selected from the 4 periods and groups 3 to 12 of the periodic table (according to the IUPAC nomenclature of Inorganic Chemistry 1989);
n is 2 or 4;
m is 2;
s is 0 or 2;
m + s = n;
Each R < ^{1 >} is independently a linear or branched (C1-C30) alkyl group;
Each R < ³ > is independently a linear or branched (C1-C30) alkyl group; And
Each R ⁴ is independently O _w -R ^{1 "} , wherein w is 0 or 1, R ^1" is a linear or branched (C ¹ -C 30) alkyl group, or
- linear or branched (C1-C20) alkyl (O- (C1-C20) alkyl) _p, (C1-C20) alkyl (O- (C1-C20) alkenyl) _p or (C1-C20) alkyl, -O (C1-C20) alkyl) _e (C1-C20) alkenyl) _f, wherein each p is independently 1, 2 or 3, each e is independently 0, 1 or 2, and each f is independently 0, 1 or 2;
Where each p is independently 1 or 2;
- -OC (= O) -R2, -OP (= O) 2 -R2, -OPR 6 (= O) OP (= O) (O-R2) 2 ( where R ⁶ is as defined in the claim 1, wherein (= O) (OR ⁶ ) O-R 2 (wherein R ⁶ is as defined in the above 1), or -OS (= O) ₂ -R ₂ ; The R2 moiety is independently
A substituted or unsubstituted, saturated or partially unsaturated hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S; or
- a substituted or unsubstituted aromatic hydrocarbyl group optionally comprising at least one heteroatom selected from N, O, P or S; or
- = O; Which is a hydrolyzable group for Broensted acid selected from < RTI ID = 0.0 >
cable.
The method of claim 1, wherein the silanol condensation catalyst compound (b) is a subgroup of a compound of formula (Ic) (also referred to as a compound of formula (Icc)
Me is selected from Ti, Zr, Hf, Cu or Zn;
n is 2 or 4;
m is 2;
s is 0 or 2;
m + s = n;
Each R < ^{1 >} is independently a linear or branched (C1-C30) alkyl group;
Each R < ³ > is independently selected from a linear or branched (C1-C30) alkyl group;
Each R ⁴ is O _w -R ^{1 "} , wherein w is 0 or 1, R ^1" is a linear or branched (C ¹ -C 30) alkyl group, or
- linear or branched (C1-C20) alkyl (O- (C1-C20) alkyl) _p, (C1-C20) alkyl (O- (C1-C20) alkenyl) _p or (C1-C20) alkyl, -O (C1-C20) alkyl) _e (C1-C20) alkenyl) _f, wherein each p is independently 1, 2 or 3, and each e is independently 0, 1 or 2, and each f is independently selected from 0, 1,
cable.
The method of claim 1, wherein the "optionally substituted," the number of one to four, "optional substituent" is -OH, -NH _2, = NH, nitro (nitro), chiol (thiol), Bang C _1-12 alkyl ( thioC _1-12 alkyl), CN or halogen such as -F, -Cl, -Br or -I, -COR ', -CONR' ₂ , -COOR 'wherein each R' is independently H or C1-C12) alkyl.
The process for producing a silanol condensation catalyst according to claim 1, wherein the silanol condensation catalyst compound (b) of the formula (I) is a silanol condensation catalyst compound having a hydrolyzable silanol group, Lt; RTI ID = 0.0 >%< / RTI > by weight.
The method of claim 1, wherein the polyethylene (a) containing the hydrolyzable silane group is a copolymer of ethylene having a silane group containing a comonomer and optionally other comonomers; Or a homopolymer or copolymer of ethylene having silane groups introduced into the polyethylene polymer by grafting of the silane group comprising the compound.
The process according to claim 1, wherein the polyethylene (a) containing the hydrolyzable silane group is polyethylene prepared in the presence of an olefin polymerization catalyst or a polyethylene produced in a high pressure production process, which contains a hydrolyzable silane group.
cable.
The cable according to claim 1, wherein the polymer composition comprises, based on the total amount of the polymer composition, a hydrolyzable silane group in an amount of 0.001 to 12 mol%.
The method of claim 1, wherein the polyethylene (a) is LDPE having a density of from 900 to 945 kg / m 3;
Wherein said silanol condensation catalyst compound (b) is a compound of formula (Ic);
Me ^{+ n} (OCR ¹ = CH-C (C = O) R ³ ) _m R ⁴ _s (Ic)
Where Me is a metal selected from Groups 3 to 12 of the Periodic Table (according to Inorganic Chemistry 1989 IUPAC nomenclature);
n is 2 or 4;
m is 2;
s is 0 or 2;
m + s = n;
Each R < ^{1 >} is independently a linear or branched (C1-C6) alkyl group;
Each R < ³ > is independently a linear or branched (C1-C6) alkyl group;
Each R ⁴ is O _w -R ^{1 "} , wherein w is 0 or 1, and R ^1" is selected from a linear or branched (C 1 -C 6)
cable.
The cable according to claim 1,
A cable (A) comprising a conductor surrounded by at least an insulator layer comprising a polymer composition as defined in claim 1, or
A power cable, selected from a cable (B) comprising a conductor, surrounded by an inner semiconductor layer, an insulator layer and an outer semiconductor layer, wherein at least one layer comprises a polymer composition as defined in claim 1,
cable.
A method of making a cable according to claim 1, comprising applying at least one layer to a conductor, wherein at least one layer is a layer comprising a composition as defined in claim 1.
12. The method of claim 11, wherein the method comprises the additional step of cross-linking one or more obtained layers comprising a polymer composition as defined in claim 1 in the presence of water. .
A cross-linked cable obtained by the manufacturing method according to claim 12.
(a) an LDPE copolymer having a density of 900 to 945 kg / m < ³ > and the following compound;
CH ₂ = CH- (CH ₂ ) _t -Si (OA) ₃ (IIc),
Where t is from 0 to 6;
A is a hydrocarbyl group, formyl group or acetyl group; And
(b) a silanol condensation catalyst compound of formula (I) as defined in claim 1.
A product comprising a polymer composition as defined in claim 1.
Use of a silanol condensation catalyst compound of formula (I) as defined in claim 1 for cross-linking of polyethylene (a) containing hydrolysable silane groups, as defined in claim 1.
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